CN100593549C - Method for improving the wear resistance of rare earth auxiliary agent modified rubber - Google Patents
Method for improving the wear resistance of rare earth auxiliary agent modified rubber Download PDFInfo
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- CN100593549C CN100593549C CN200810190760A CN200810190760A CN100593549C CN 100593549 C CN100593549 C CN 100593549C CN 200810190760 A CN200810190760 A CN 200810190760A CN 200810190760 A CN200810190760 A CN 200810190760A CN 100593549 C CN100593549 C CN 100593549C
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Abstract
The invention relates to a method for improving abrasive resistance of rubber through modification of rubber by rare-earth addition agent, belonging to a rubber addition agent and rubber preparation field. By using big specific surface area and super fine rare-earth oxide as the rubber addition agent, the invention uses organic modifying agent to modify rare-earth oxide, then being used as rubberaddition agent to add into the rubber for modification of the rubber in order to strengthen pressure performance of the rubber, particularly to improve abrasive resistance of the rubber. The method for improving abrasive resistance of rubber through modification of rubber by rare-earth addition agent has the advantages of simple technology, being easy to operate, low cost and making rubber products suitable to the use of tire rubber, etc.
Description
One, technical field
The present invention relates to the method that the rare-earth additive modified rubber improves rubber abrasive-resistance, belong to rubber ingredients and rubber preparation field.
Two, background technology
Material is the basic substance and the guide of social production and technical progress, the macromolecular material industry that eighties of last century grows up has brought huge material progress to human society, rubber is as the important component part of macromolecular material, have the irreplaceable specific function of other material at the tire manufacture view, become indispensable important substance in national economy and the daily life.Progress along with expanding economy and society, people are more and more higher to the requirement of rubber item, as: mechanical properties such as the wear resistance of rubber for tire, elasticity there has been higher requirement, traditional rubber ingredients improve limited to its mechanical property, present technology has not satisfied this requirement, so be badly in need of the new rubber ingredients of exploitation, improve the use properties of rubber.
The existing very long research history of the filling-modified research of rare earth rubber ingredients, rare earth element since its unique character add to its unique effect arranged in the rubber.The main effect of rare earth element has the sulfuration of promotion, antifatigue, raising thermostability, strengthening action, fire retardation etc.Rare-earth additive is nontoxic, can significantly improve the mechanical property of rubber, and consumption is few, and price is low, can satisfy the particular requirement of rubber mechanical property.Rare-earth additive is initial fills mainly with increment, reduces cost is purpose, along with the development of Materials science, and the exploitation of ultrafine particle, the direction of filling to other excellent properties such as strengthening, toughness reinforcing develops.The importance that nano material is used in rubber is to make the high-performance supporting material, studies show that nano material can play strengthening action to rubber, and the nano material of up to the present using in rubber mainly contains Al
2O
3, TiO
2, SiO
2, CaCO
3With carbon black etc.Rare earth nano material integrates rare earth characteristic and nano-meter characteristic, replenishes mutually, carries forward, and is " Te-Te " combination, brings out the best in each other, and will inevitably start out the comprehensive good characteristic that non-rare earth nano material and rare earth non-nano material are not had.Therefore but rare earth material is poor as the consistency between inorganic material and elastomeric material, is difficult to guarantee the good affinity of the two-phase interface of matrix material, makes the application in rubber of rare earth material be subjected to great restriction.For this reason, organic modification is carried out on reply rare earth surface, solves above-mentioned topic.Two kinds of very big material interfaces of performance difference are coupled together, thereby improve the infill system consistency, improve composite property.
The sharp CN101134819A of China has reported the method for rare earth or transition metal doping carbon black modified rubber, and the stress at definite elongation and the tensile strength of resulting cross-linked rubber are improved, but do not change the wear resisting property of rubber.Chinese patent CN1219553A has reported that vulcanization acceralator for rare earth rubber can promote the vulcanization of rubber, but the mechanical property aspect that improves rubber is not become effective.Chinese patent CN1903924A has reported a kind of rubber accelerator, can improve thermal conduction and thermal diffusivity in the vulcanization of rubber process, shortens curing time more than 30%, but does not also relate to its mechanical property.
Three, summary of the invention
The purpose of this invention is to provide and a kind of rubber is carried out modification, the rare-earth additive modified rubber that improves rubber abrasive-resistance improves the method for rubber abrasive-resistance.
For achieving the above object, the present invention is by the following technical solutions and processing step:
(1) at first adopts specific surface area 〉=50m
2G
-1, volume center directly is 5～0.01 μ m, the superfine rare-earth oxide compound of 2～0.05 μ m particularly, and this rare earth oxide is La
2O
3, CeO
2, Pr
6O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3, Y
2O
3And Sc
2O
3In one or more mixed rare-earth oxide.CeO particularly
2, or contain CeO
2Mixed rare-earth oxide.
(2) get the organic modifiers of bigger serface, superfine rare-earth oxide mass 0.5～10%, as, Sulfonates, sulfuric acid ester, phosphoric acid ester anion surfactant; And silane coupling agent, titanate coupling agent, aluminate coupling agent.Being made into concentration is 0.1～10% solution, and water-soluble can be made into the aqueous solution, water-fastly can be made into alcoholic solution.Adopt the wet method surface treatment, rare earth oxide is distributed in the organically-modified agent solution, stirring, filtration, drying, the rare-earth additive of the surface modification that obtains organising.
(3) then the rare earth oxide behind the organic modification is joined in the rubber batching, the add-on of rare-earth additive is 0.5～5% of a rubber quality.Plasticate, mixing, sulfidization molding.Used rubber is synthetic rubber such as natural rubber and styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, polyisoprene rubber, different third rubber.
Because bigger serface, superfine rare-earth particle microcosmic form stronger combining with rubber polymer after being distributed to rubber inside, simultaneously because the small-size effect of ultrafine particle and surface effects etc., make rare earth ion and the polymkeric substance place of combination almost unstressed concentrated, and rare earth ion and polymkeric substance are combined firmly.By rare earth ion is carried out organic modification of surface, make it more can form stronger combining in addition, improve the mechanical property of rubber polymer with rubber.Therefore, the superfine rare-earth auxiliary agent through the surface modification that organises adds in the rubber, makes rubber have very high compactness and good mechanical property, particularly good wear resistance.
The present invention has following characteristics:
1, technology is simple, and easy handling is easy to suitability for industrialized production.
2, the rare-earth additive surface modification that organises, dispersion effect is good, and cost is low.
3, bigger serface, superfine rare-earth auxiliary agent and the rubber polymer that organises after the surface modification is combined, and is of value to the performance of performance bigger serface, superfine rare-earth material, improves the mechanical property, particularly wear resisting property of rubber.
Four, embodiment
Embodiment 1:
Add in the natural rubber with bigger serface, fine cerium oxide.
Taking by weighing the 25g Sodium dodecylbenzene sulfonate and be dissolved in the 2500mL water, is 78.32m with the 1kg specific surface area
2G
-1, D
50Be that 0.78 μ m cerium oxide is put into sodium dodecyl sulfate solution, 50 ℃ are stirred down 2h, filter then, drying, the cerium oxide of the surface modification that obtains organising.Keeping on natural rubber original formulation and the technical process basis of invariable, cerium oxide behind the organic modification is joined in 80Kg (quality with natural rubber the is a benchmark) natural rubber, plasticate, mixing, sulfidization molding, make rubber sample by national standard, test then.Test result is as shown in the table:
Embodiment 2:
Add in the styrene-butadiene rubber(SBR) with bigger serface, ultra-fine mixing lanthanum cerium oxide.
Taking by weighing the 60g sodium lauryl sulphate and be dissolved in the 3000mL water, is 52.26m with the 3kg specific surface area
2G
-1, D
50Be that 1.56 μ m mixing lanthanum cerium oxides are put into sodium dodecyl sulfate solution, 40 ℃ are stirred down 4h, filter then, drying, the mixing lanthanum cerium oxide of the surface modification that obtains organising.Keeping on natural rubber original formulation and the technical process basis of invariable, mixing lanthanum cerium oxide behind the organic modification is joined in 120Kg (quality with styrene-butadiene rubber(SBR) the is a benchmark) styrene-butadiene rubber(SBR), plasticate, mixing, sulfidization molding, make rubber sample by national standard, test then.Test result is as shown in the table:
Embodiment 3:
Add in the natural rubber with bigger serface, ultra-fine mixing LaCePrNd oxide compound.
Taking by weighing 40g composite titanium acid esters coupling agent and be dissolved in the 1500mL water, is 63.45m with the 1.2kg specific surface area
2G
-1, D
50Be that 0.26 μ m mixing LaCePrNd oxide compound is put into composite titanium acid esters coupling agent solution, 60 ℃ are stirred down 6h, filter then, drying, the mixing LaCePrNd oxide compound of the surface modification that obtains organising.Keeping on natural rubber original formulation and the technical process basis of invariable, mixing LaCePrNd oxide compound behind the organic modification is joined in 60Kg (quality with natural rubber the is a benchmark) natural rubber, plasticate, mixing, sulfidization molding, make rubber sample by national standard, test then.Test result is as shown in the table:
Claims (8)
1, the rare-earth additive modified rubber improves the method for rubber abrasive-resistance, it is characterized in that: make rubber ingredients with bigger serface, superfine rare-earth oxide compound, get the organic modifiers of rare-earth oxidation amount 0.5～10%, it is 0.1～10% solution that organic modifiers is made into mass concentration, rare earth oxide is distributed in the organically-modified agent solution, stirring, filtration, drying, the rare-earth additive of the surface modification that obtains organising; The rare-earth additive of surface modification is joined in the rubber batching, and the add-on of rare-earth additive is 0.5～5% of a rubber quality, plasticates, mixing, sulfidization molding, and described rare earth oxide is bigger serface, superfine powder, its specific surface area 〉=50m
2G
-1, its volume center footpath D
50Be 2～0.05 μ m, described organic modifiers is Sulfonates, sulfuric acid ester or phosphoric acid ester anion surfactant.
2, rare-earth additive modified rubber according to claim 1 improves the method for rubber abrasive-resistance, and it is characterized in that: rare earth oxide is La
2O
3, CeO
2, Pr
6O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3, Y
2O
3And Sc
2O
3In a kind of.
3, rare-earth additive modified rubber according to claim 1 improves the method for rubber abrasive-resistance, and it is characterized in that: rare earth oxide is La
2O
3, CeO
2, Pr
6O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3, Y
2O
3And Sc
2O
3In more than one mixed rare-earth oxide.
4, rare-earth additive modified rubber according to claim 2 improves the method for rubber abrasive-resistance, and it is characterized in that: rare earth oxide is CeO
2
5, rare-earth additive modified rubber according to claim 3 improves the method for rubber abrasive-resistance, and it is characterized in that: rare earth oxide is for containing CeO
2Mixed rare-earth oxide.
6, rare-earth additive modified rubber according to claim 1 improves the method for rubber abrasive-resistance, it is characterized in that: organic modifiers is water-soluble is made into the aqueous solution, the water-fast alcoholic solution that is made into.
7, rare method that additive modification rubber improves rubber abrasive-resistance that goes up according to claim 1, it is characterized in that: described rubber is natural rubber or synthetic rubber.
8, rare-earth additive modified rubber according to claim 7 improves the method for rubber abrasive-resistance, and it is characterized in that: synthetic rubber is styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, polyisoprene rubber or different third rubber.
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|---|---|---|---|
| CN200810190760A CN100593549C (en) | 2008-12-25 | 2008-12-25 | Method for improving the wear resistance of rare earth auxiliary agent modified rubber |
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|---|---|---|---|
| CN200810190760A CN100593549C (en) | 2008-12-25 | 2008-12-25 | Method for improving the wear resistance of rare earth auxiliary agent modified rubber |
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| CN100593549C true CN100593549C (en) | 2010-03-10 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146116A (en) * | 2013-03-15 | 2013-06-12 | 东风(十堰)非金属部件有限公司 | Rare-earth modified polypropylene resin and preparation method thereof |
| CN103756079B (en) * | 2014-01-28 | 2015-12-02 | 内蒙古科技大学 | Composite modified cerium oxide improves the method for kiss-coating grip-pad rubber performance |
| CN104045868B (en) * | 2014-06-16 | 2016-08-24 | 中国热带农业科学院农产品加工研究所 | A kind of preparation method of nano-cerium oxide/native rubber composite material |
| CN104311895B (en) * | 2014-10-13 | 2016-03-16 | 安徽奥丰汽车配件有限公司 | Automobile rubber flexible coupling sizing material |
| CN106277020A (en) * | 2015-06-12 | 2017-01-04 | 常州卓煜新材料科技有限公司 | A kind of bigger serface micron cerium oxide preparation method |
| CN105348583A (en) * | 2015-12-10 | 2016-02-24 | 定远县杰仕达体育用品有限公司 | Ball type inner container flexible anti-wear material |
| CN105348584A (en) * | 2015-12-10 | 2016-02-24 | 定远县杰仕达体育用品有限公司 | Ball type high-elasticity inner container |
| CN105348582A (en) * | 2015-12-10 | 2016-02-24 | 定远县杰仕达体育用品有限公司 | Rubber coating material for ball type outer skin |
| CN106009043B (en) * | 2016-05-30 | 2021-08-13 | 内蒙古科技大学 | Modified rare earth sulfide auxiliary agent, preparation method thereof and rubber preparation method |
| CN107461297A (en) * | 2017-10-16 | 2017-12-12 | 派腾奥普科技服务（北京）有限公司 | A kind of tidal power generating device |
| CN107903455A (en) * | 2017-11-08 | 2018-04-13 | 广西融辰建设工程有限公司 | A kind of radiation resistant rubber and preparation method thereof |
| CN110295414B (en) * | 2019-06-25 | 2021-12-31 | 海南经纬乳胶丝有限责任公司 | Environment-friendly energy-saving latex yarn product and preparation method thereof |
| CN111393727A (en) * | 2020-03-10 | 2020-07-10 | 泉州市华创园智能研究有限公司 | Wear-resistant rare earth rubber material and preparation method thereof |
-
2008
- 2008-12-25 CN CN200810190760A patent/CN100593549C/en not_active Expired - Fee Related
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